US20180291195A1

US20180291195A1 - Electrically insulating thermally conductive polymer resin composition based on styrenics with balanced properties

Info

Publication number: US20180291195A1
Application number: US15/766,143
Authority: US
Inventors: Tobias Schulz; Norbert Niessner; Gisbert Michels; Janna MICHAELIS DE VASCONCELLOS; Hans-Werner Schmidt; Florian WIEBERGER; Tristan KOLB
Original assignee: Ineos Styrolution Group GmbH
Current assignee: Ineos Styrolution Group GmbH
Priority date: 2015-10-09
Filing date: 2016-10-06
Publication date: 2018-10-11
Also published as: ES2768983T3; EP3359593A1; EP3359593B1; WO2017060347A1

Abstract

Thermally conductive polymer (TCP) resin composition (i) or (ii) are described, comprising components (I) and (II): (i) 40 to 72% by volume of at least one matrix polymer (I); 28 to 60% by volume of a thermally conductive filler material (II) (D₅₀0.1 to 200 μm) consisting of aluminosilicate (II-1) in combination with a further component (II-2) selected from: multi wall carbon nanotubes, graphite and and boron nitride, wherein the volume ratio (ll-1)/(ll-2) is 30:1 to 0.1:1; or (ii) 40 to 65% by volume of at least one matrix polymer (I); 35 to 60% by volume of aluminosilicate (II) (D₅₀0.1 to 200 μm); wherein the matrix polymer (I) comprises styrenic polymers (I′) selected from: ABS resins, ASA resins, and elastomeric block copolymers. Shaped articles made thereof can be used as “Cool Touch” surfaces for automobile interior, motor housings, lamp housings and electrical and electronic housings and as heat sinks for high performance electronics or LED sockets.

Description

The present invention deals with a thermoplastic polymer resin composition with high thermal conductivity and high melt flow, suitable for extrusion, and a low electrical conductivity. The thermally conductive polymer (TCP) resin composition comprises a matrix polymer based on styrenic polymers (styrenics), in particular styrene copolymers. Further aspects of the invention are a process for the preparation of the TCP resin composition, shaped articles comprising the TCP-composition and the use of the TCP-composition for several applications such as “Cool Touch” surfaces for automobile interior, a heat sink for high performance electronics or for LED sockets or electrical and electronic housings.
Many electrical and electronic devices include a light emitting package in a structure such as a mold frame, a chassis structure or a metal bottom cover. Because of their excellent mechanical properties, thermoplastic polymeric resin compositions are used to manufacture articles of various sizes and shapes, including without limitation chassis components, and housings. In many cases, because of the design flexibility and their low cost, polymer resin compositions have replaced metal in these applications. However, many of these applications require that the parts be in the vicinity of or in contact with heat sources such as electrical lights. It is therefore desirable to form these parts from materials that are sufficiently thermally conductive to dissipate the heat generated. In an attempt to improve thermal conductive characteristics, it has been the conventional practice to add thermally conductive materials to thermoplastic compositions.
WO 2014/202649 discloses thermally conductive polymer/boron nitride compounds which comprise a thermoplastic polymer, boron nitride agglomerate, a reinforcing filler and optionally at least one further thermally conductive filler selected from powdered metal, carbon in the form of graphite, and ceramic fillers and mineral fillers. As thermoplastic polymer polyamide is preferably used, thermoplastic polymers made from vinylaromatic monomers are not explicitly mentioned. A combination of polyamide 6, boron nitride hybride flakes, aluminosilicate and glass fibers is most preferred.
KR-A-20100061082 discloses a thermally conductive polymer composition comprising 56-64 vol.-% ceramic filler particles and 0.9-1 vol.-% multi-walled carbon nanotube particles, each based on the volume of the polymer resin.
The polymer resin having a low viscosity is an epoxy-, phenol- or polyvinylidene fluoride resin.
US-A-2012/0157600 describes a molded thermoplastic article comprising a thermoplastic polymer, a thermally conductive filler and carbon black powder. As thermally conductive fillers a variety of flakes and fibers composed of oxides, nitrides, metals and carbon is mentioned, graphite being in particular preferable. Among the suitable thermoplastic polymers syndiotactic polystyrene is listed, but polyesters and polyamides are preferred. The composition is used for motor housings, lamp housings and electrical and electronical housings.
KR-A-20130088251 deals with a thermally conductive material comprising a thermoplastic resin selected from polyolefins, polyamides, polybutyleneterephthalates, acrylonitrile-butadiene-styrene copolymers, polycarbonates, polyesters, polyphenylenesulfides and thermoplastic elastomers, and graphite and/or boriding nitrogen as thermoplastic conductive filler. Preferably as thermoplastic resins PP, PA6 or PBT are used in combination with expanded graphite or boriding nitrogen, optionally in combination with low amounts of carbon multi wall nanotubes.
KR-A-20090001068 discloses a thermally conductive thermoplastic resin composition comprising 100.0 parts by weight of a base resin and 0.1-30 parts by weight of a thermal conductive additive. The base resin comprises a grafted acrylonitrile—styrene-butadiene (ABS) copolymer resin (A) and a styrene-acrylonitrile (SAN) copolymer (B). The thermally conductive additive is a low melting point metal and/or a ceramic fiber, in particular alumina fiber.
US-2002/0058743 discloses a thermally conductive polymer composition comprising a polymer matrix, preferably made from a thermoplastic resin or thermoplastic elastomer, and graphitized carbon fibers and optionally a thermally conductive filler that is electrically insulative (e.g. BN, natural graphite, SiC). In a long list of suitable resins inter alia styrene acrylonitrile copolymer, ABS resin, and styrene-butadiene block copolymers are listed. One composition contains a styrene thermoplastic elastomer, graphitized carbon fibers, boron nitride and aluminum hydroxide.
US-2014/0240989 describes thermally conductive polymers comprising a thermoplastic polymer and a thermally conductive material such as AlN, BN, MgSiN₂, SiC and/or graphite. In a long list of suitable polymers inter alia polystyrenes and ABS and blends of ABS are mentioned, polyamides are in particular preferred.
The afore-mentioned currently available thermally conductive thermoplastic resin compositions are often difficult to process in particular by injection molding due to high shrinkage and often show minor surface quality.
Thus, there is still a need for thermally conductive materials with a high thermal conductivity and a low electrical conductivity, which are suitable for injection molding, possessing balanced properties in respect to shrinkage, surface gloss and processability. Therefore, it is an object of the invention to provide a thermally conductive polymer resin composition having the afore-mentioned properties.
It was surprisingly found that the problem mentioned above can be solved by the inventive TCP resin composition according to the claims.
One aspect of the invention is a thermally conductive polymer (TCP) resin composition (i) or (ii) comprising (or consisting of) components (I) and (II):

- (i) 40 to 72% by volume of at least one matrix polymer (I) as component (I); and
  - 28 to 60% by volume of a thermally conductive filler material (II) as component (II) having a weight median particle diameter (D₅₀) of from 0.1 to 200 μm, which consists of at least one aluminosilicate as component (II-1) in combination with at least one further component (II-2) selected from the group consisting of: multi wall carbon nanotubes, graphite and boron nitride,
  - wherein the volume ratio between components (II-1) and (II-2) is from 30:1 to 0.1:1, preferably 15:1 to 0.1:1, more preferably 10:1 to 0.1:1; or
- (ii) 40 to 65% by volume of at least one matrix polymer (I) as component (I); and
  - 35 to 60% by volume of at least one aluminosilicate as thermally conductive filler material component (II), having a weight median particle diameter (D₅₀) of from 0.1 to 200 μm;
- wherein the matrix polymer (I) comprises styrenic polymers (I′) selected from the group consisting of: ABS (acrylonitrile-butadiene-styrene) resins, ASA (acrylonitrile-styrene-acrylate) resins, and elastomeric block copolymers of the structure (S-(B/S))_n-S,
- where S is a vinylaromatic block forming a hard phase, (B/S) is a random copolymer block of vinylaromatic monomer and of a conjugated diene forming a soft phase, and n are natural numbers from 1 to 10, wherein the elastomeric block copolymer has a monomer composition comprising 25 to 60% by weight (based on the elastomeric block copolymer) of diene and 75 to 40% by weight (based on the elastomeric block copolymer) of vinylaromatic compound, the glass transition temperature Tg of block S is above 25° C. and that of block (B/S) is below 25° C., and the proportion of the hard phase in the elastomeric block copolymer is from 5 to 40% by weight and the relative amount of 1,2 linkages of the polydiene, based on the sum of 1,2- and 1,4-cis/trans-linkages, is less than 15%; and
- wherein the sum of components (I) and (II) totals 100% by volume.

In a cumulative particle size distribution the ordinate represents the cumulative size distribution from 0% to 100% and the abscissa represents the particle size. The particle size corresponding to an ordinate value of 50% is called D₅₀.
The particle sizes of component (II) can be measured using mesh analysis (e.g. Retsch AS 200 jet), dynamic image analysis (e.g. Retsch Camsizer XT), Transmission Electron Microscopy (TEM) and/or laser light scattering (e.g. Horiba LA-300).
In principle, the inventive TCP resin composition can optionally comprise at least one further common additive and/or auxiliary as component (III). Component (III) is, if present, different from components (I) and (II). Said additives and/or auxiliaries (III) may be present in the inventive polymer blend in low amounts, such as 0.1 to 5% by weight, preferably 0.1 to 3% by weight, based on the entire inventive TCP resin composition. Suitable further additives and/or auxiliaries (III) are such as common plastic processing aids, plasticizers, waxes, antioxidants, mineral oil, silicone oil, heat- and/or UV-stabilizers, flame-retardants, dyes and pigments, in particular plastic processing aids such as antioxidant agents and lubricants. Often pigments are added.
Preferably the afore-mentioned inventive TCP resin composition does not comprise further additives and/or auxiliaries (III).
The inventive TCP resin composition generally has a thermal conductivity κ of more than 0.5 W/m·K, preferably more than 0.7 W/m·K, more preferably more than 0.9 W/m·K, most preferred more than 1.0 W/m·K.
The thermal conductivity is defined as κ=α·c_p·ρ and is determined as follows:

- thermal diffusivity α: determined by Laser flash analysis (XFA 500 XenonFlash apparatus (Linseis) with an InSb infrared detector)
- specific heat c_pis determined by DSC (TA Instruments Q1000 DSC), ASTM E1269
- density ρ is determined by Buoyancy Balance (Mettler Toledo AG245)

Further the shrinkage usually is less than 7%, preferably less than 3%, more preferred less than 1% (determined from the density difference of solid material and corresponding melt).
All cited standards for any measurement methods refer to the current issue of the cited standard valid at the priority date.
The invention also includes the combination of different inventive embodiments.
According to one embodiment, preferably the TCP resin composition (i) comprises (or consists of) components (I) and (II) in the following amounts:
Component (I) 55 to 72% by volume,
Component (II) 28 to 45% by volume,
wherein the sum of components A) and B) totals 100% by volume.
According to one further embodiment, more preferably the TCP resin composition (i) comprises (or consists of) components (I) and (II) in the following amounts:
Component (I) 59 to 72% by volume,
Component (II) 28 to 41% by volume,
wherein the sum of components A) and B) totals 100% by volume.
According to one further preferred embodiment, provided that component (II-2) is multi wall carbon nanotubes or graphite, the TCP resin composition (i) comprises (or consists of) components (I) and (II) in the following amounts:
Component (I) 55 to 65%, preferably 59 to 65% by volume,
Component (11) 35 to 45%, preferably 35 to 41% by volume,
wherein the sum of components A) and B) totals 100% by volume.
According to one further embodiment, preferably the TCP resin composition (ii) comprises (or consists of) components (I) and (II) in the following amounts:
Component (I) 45 to 60% by volume,
Component (II) 40 to 55% by volume,
wherein the sum of components (I) and (II) totals 100% by volume.

Component (I)

Suitable components (I) or matrix polymers (I) comprise (consist of) at least one styrenic polymer (I′) selected from the group consisting of: ABS (acrylonitrile-butadiene-styrene) resins, ASA (acrylonitrile-styrene-acrylate) resins, and the above-mentioned elastomeric block copolymers of the structure (S-(B/S))_n-S.
Additionally the matrix polymer (I) can optionally comprise (consist of) at least one further thermoplastic polymer (I″) selected from the group consisting of: polycarbonates and polyamides.
Preferably the matrix polymer (I) comprises or consists of one styrenic polymer (I′) optionally in a mixture with one of said further thermoplastic polymers (I″). If the matrix polymer (I) comprises a further thermoplastic polymer (I″), the styrenic polymer (I′) is preferably an ABS resin or ASA resin.
More preferably the matrix polymer (I) comprises or consists of at least one—preferably exactly one —: ABS resin, ASA resin, elastomeric block copolymers of the structure (A(B/A))_n-A, blend of ABS resin with polycarbonate (PC), blend of ABS resin with polyamide (PA), blend of ASA resin with polycarbonate (PC), or blend of ASA resin with polyamide (PA).
The afore-mentioned term “blend” means a mixture of one or more, preferably one, of the styrenic polymers (I′) and one or more, preferably one, of the further thermoplastic polymers (I″). The blend may be obtained by combining said polymers (I′) and (I″) using any melt-mixing method. Preferably said polymers (I′) and (I″) are used as a ready mix blend of the matrix polymer (I) which may then be used for the manufacture of the inventive TCP resin composition. Alternatively for the manufacture of the inventive TCP resin composition said polymers (I′) and (I″) can be used individually and may be added simultaneously or successively to a compounder to form a melt-mixed blend of the matrix polymer (I).
According to a first preferred embodiment the matrix polymer (I) is an ABS resin.
According to a second preferred embodiment the matrix polymer (I) is an ASA resin.
According to a third preferred embodiment the matrix polymer (I) is an elastomeric block copolymer of the structure (A-(B/A))_n-A.
According to a fourth preferred embodiment the matrix polymer (I) is a blend of an ABS resin with polycarbonate.
According to a fifth preferred embodiment the matrix polymer (I) is a blend of an ABS resin with polyamide.
According to a sixth preferred embodiment the matrix polymer (I) is a blend of an ASA resin with polycarbonate.
According to a seventh preferred embodiment the matrix polymer (I) is a blend of an ASA resin with polyamide.
The afore-mentioned matrix polymers (I) are commonly known to a person skilled in the art and are commercially available. Typical examples of suitable commercially available products are such as Terluran® GP22 (ABS); Terluran HI-10 (ABS); Luran® S 797 (ASA); Luran S 778T (ASA); Luran S 757 (ASA); Terblend® N NM-21 EF (ABS/PA); Terblend S NM-31 (ASA/PA); Luran S KR2864C (ASA/PC), Novodur® P2H-AT (ABS), Novodur Ultra (ABS/PC) and Styroflex® 2G66 (styrenic block copolymer (SBC)) all of which are obtainable from Styrolution company (Frankfurt, Germany).
Among the afore-mentioned products Terluran® GP22, Terluran® HI-10 Terblend® N NM-21 EF and/or Styroflex® 2G66 is preferably used as matrix polymer (I). More preferred as matrix polymer (I) is Terluran® HI-10, Terblend® N NM-21 EF and/or Styroflex® 2G66. Each of the afore-mentioned products can be used in mixture with each other or, preferably, alone.
Suitable ABS resins used as styrenic polymer (I′) comprise at least one, preferably one, graft copolymer (I′-1) of a diene-based rubber and at least one, preferably one, rubber free vinyl copolymer (I′-2). The graft copolymer (IA) is based on a diene-rubber, in particular a butadiene rubber, upon which a mixture of at least one vinylaromatic monomer, in particular styrene, and acrylonitrile and optionally further monoethylenically unsaturated monomers is grafted.
The rubber free vinyl copolymer (I′-2) is in particular a copolymer made from at least one, preferably one vinylaromatic monomer such as styrene or alpha methyl styrene, and acrylonitrile and optionally an additional monoethylenically unsaturated monomer.
The rubber free copolymer (I′-2) is preferably a copolymer made from styrene and acrylonitrile (SAN-copolymer) or a copolymer made from alpha methyl styrene and acrylonitrile (AMSAN-copolymer).
The graft copolymer (IA) is usually embedded in a matrix made from the rubber free vinyl copolymer (I′-2).
An ABS resin (I′) comprising (or consisting of) an ABS graft copolymer (I′-1) and a styrene-acrylonitrile (SAN) copolymer (I′-2) is preferred. Such an ABS resin (I′) is commercially available e.g. from Styrolution company as Terluran® GP22 (ABS) and Terluran HI-10 (ABS).
Preferred SAN-copolymers or AMSAN-copolymers (I′-2) comprise (consist of) generally 18 to 35 wt.-%, preferably 20 to 32 wt.-%, particular preferably 22 to 30 wt.-% acrylonitrile (AN), and 82 to 65 wt.-%, preferably 80 to 68 wt.-%, particular preferably 78 to 70 wt.-% styrene (S) or alpha methyl styrene (AMS), wherein the sum of the amounts of styrene or alpha methyl styrene and acrylonitrile totals 100 wt.-%.
Said SAN copolymers (I′-2) are also known and commercially available as for example Luran® 358 N (VLM); Luran 251000, Luran 2580 from Styrolution company.
Said AMSAN copolymers (I′-2) are commercially available as for example Luran HH-120 from Styrolution company.
According to the invention ABS resins (I′) as herein before and hereinafter described are preferred which comprise (consist of) from 5 to 80%, preferably from 15 to 60%, particularly preferably from 35 to 55%, most preferably 40 to 50% by weight, based on the total of components (I′) by weight of a graft polymer (I′-1) and from 20 to 95%, preferably from 40 to 85%, particularly preferably from 45 to 65%, most preferably 50 to 60% by weight by weight of a rubber free vinyl copolymer (I′-2).
In particular preferred is an ABS resin (I′) comprising components (I′-1) and (I′-2),

(I′-1) from 5 to 80% by weight, based on (I′), of a graft polymer (I′-1) having monomodal or, preferred, bimodal particle size distribution made from,
a1) 40 to 90% by weight of an elastomeric particulate graft base a1), obtained by polymerization of, based on a1),
- a11) from 70 to 100% by weight of at least one conjugated diene, in particular butadiene,
- a12) from 0 to 30% by weight of at least one other monoethylenically unsaturated monomer and
- a13) from 0 to 10% by weight of at least one polyfunctional, crosslinking monomer and
a2) from 10 to 60% by weight of a graft a2) made from, based on a2),
- a21) from 65 to 95% by weight of at least one vinylaromatic monomer, in particular styrene,
- a22) from 5 to 35% by weight of acrylonitrile,
- a23) from 0 to 30% by weight of at least one other monoethylenically unsaturated monomer, and
- a24) from 0 to 10% by weight of at least one polyfunctional, crosslinking monomer and
(I′-2) from 20 to 95% by weight of a thermoplastic polymer (I′-2) having a viscosity number VN (determined according to DIN 53726 at 25° C., 0.5% by weight in dimethylformamide) of from 50 to 120 ml/g, made from, based on (I′-2),
- a21) from 69 to 81% by weight of at least one vinylaromatic monomer, in particular styrene,
- a22) from 19 to 31% by weight of acrylonitrile, and
- a23) from 0 to 12% by weight of at least one other monoethylenically unsaturated monomer.

Such preferred ABS resins are described in U.S. Pat. No. 6,323,279.
Graft copolymers (I′-1) can be prepared by known polymerization techniques, such as solution or bulk polymerization or emulsion polymerization.
A suitable process for the preparation of graft copolymers (I′-1) by emulsion polymerization is disclosed in detail in U.S. Pat. No. 6,323,279. Furthermore it is referred to U.S. Pat. No. 5,434,218 which discloses a suitable process for the preparation of graft copolymers (I′-1) whose rubber phases are prepared exclusively by solution or bulk polymerization.
The graft copolymer (I′-1) is then mixed with copolymer (I′-2) by usual methods. The mixing apparatuses used are those known to the person skilled in the art. Components (I′-1) and (I′-2) may be mixed, for example, by extruding, kneading or rolling them together.
Suitable ASA resins used as styrenic polymer (I′) comprise at least one, preferably one, graft copolymer (I′-3) of an acrylate-based rubber and at least one, preferably one rubber free vinyl copolymer (I′-2) as defined above.
The graft copolymer (I′-3) is based on an acrylate rubber, in particular a butyl acrylate rubber, upon which a mixture of at least one vinylaromatic monomer, in particular styrene, and acrylonitrile and optionally further monoethylenically unsaturated monomers is grafted.
The graft copolymer (I′-3) is usually embedded in a matrix made from the rubber free vinyl copolymer (I′-2).
An ASA resin (I′), comprising (consisting of) an ASA graft copolymer (I′-3) and a styrene-acrylonitrile (SAN) copolymer (I′-2) is very particular preferred and is commercially available e.g. from Styrolution company as Luran® S 797; Luran S 777 K and Luran S 757.
Furthermore preferred are ASA resins (I′) comprising (consisting of) a graft copolymer (I′-3) and an alpha methyl styrene-acrylonitrile (AMSAN) copolymer (I′-2) which are commercially available e.g. from Styrolution company as Luran S 778 T.
Preferably the ASA resins (I′) comprise (consist of) 29 to 46 wt.-% graft copolymer (I′-3) and 54 to 71 wt.-% rubber free vinyl copolymer (I′-2), wherein the sum of components (I′-3) and (I′-2) totals 100% by weight.
A preferred ASA graft copolymer (I′-3) is built up from

(a₃) 30 to 90% by weight, based on (I′-3), of a graft base (a₃) with a glass transition temperature (T_g) below −10° C. made from
(a₃₁) an at least partially crosslinked acrylate polymer formed from
(a₃₁₁) 50 to 99.9% by weight, based on (a₃₁), of at least one C₁-C₁₀-alkyl acrylate, in particular n-butylacrylate,
(a₃₁₂) 0.1 to 5% by weight, based on (a₃₁), of at least one polyfunctional crosslinking monomer and
(a₃₁₃) 0 to 49.9% by weight, based on (a₃₁), of a further monomer which is copolymerizable with (a₁₁₁) selected from the group consisting of the vinyl C₁-C₈-alkyl ethers, butadiene, isoprene, styrene, acrylonitrile and methacrylonitrile, and/or methyl methacrylate
(a₄) from 10 to 70% by weight, based on (I′), of a graft (a₄) with a (T_g) above 50° C., grafted onto the graft base (a₃) and built up from
(a₄₁) 50 to 95% by weight, based on (a₄), of at least one vinylaromatic monomer, in particular styrene,
(a₄₂) 5 to 50% by weight, based on (a₄), of at least one polar, copolymerizable comonomer selected from the group consisting of acrylonitrile, methacrylonitrile, C₁-C₄-alkyl (meth)acrylates, maleic anhydride and maleimides, and (meth)acrylamide, and/or vinyl C₁-C₈-alkyl ethers, or a mixture of these, in particular acrylonitrile.

Preferably said graft copolymer (I′-3) is an ASA graft copolymer, made from an at least partially crosslinked n-butyl acrylate rubber upon which styrene and acrylonitrile are grafted. Graft copolymers (I′-3) can be prepared by known polymerization techniques, such as solution or bulk polymerization or emulsion polymerization. Suitable graft copolymers (I′-3) and their preparation are disclosed in for example U.S. Pat. Nos. 5,760,134 and 6,579,937 to which is in particular referred.
Polycarbonates which are suitable for the afore-mentioned blends of ABS- or ASA-resins are described in EP-A 2537895 in paragraphs 22 to 32 to which is in particular referred.
As polycarbonate one or more, preferably one or two, more preferably one aromatic polycarbonate can be used.
According to the invention the term polycarbonate includes for example polycondensation products, for example aromatic polycarbonates, aromatic polyester carbonates.
Aromatic polycarbonates and/or aromatic polyester carbonates which are suitable according to the invention are known from the literature or may be prepared by processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, “Chemistry and Physics of Polycarbonates”, Interscience Publishers, 1964 and DE-AS 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610 and DE-A 3 832 396; for the preparation of aromatic polyester carbonates e.g. DE-A 3 077 934). The preparation of aromatic polycarbonates is carried out e.g. by reaction of diphenols with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase interface process, optionally using chain terminators, for example monophenols, and optionally using branching agents which are trifunctional or more than trifunctional, for example triphenols or tetraphenols. A preparation via a melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate is also possible.
Preferred diphenols for the preparation of the aromatic polycarbonates and/or aromatic polyester carbonates are hydroquinone, resorcinol, dihydroxydiphenols, bis(hydroxyphenyl)-C1-C5-alkanes, bis-(hydroxyphenyl)-C5-C6-cycloalkanes, bis(hydroxyphenyl)ethers, bis-(hydroxyphenyl)sulfoxides, bis-(hydroxyphenyl)ketones, bis(hydroxyphenyl)sulfones and α,α-bis-(hydroxyphenyl)-diisopropyl-benzenes and nucleus-brominated and/or nucleus-chlorinated derivatives thereof. Particularly preferred diphenols are 4,4′-dihydroxydiphenyl, bisphenol A, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfone and di- and tetrabrominated or chlorinated derivatives thereof, such as, for example, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane. 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A) is particularly preferred. The diphenols may be employed individually or as any desired mixtures. The diphenols are known from the literature or obtainable by processes known from the literature.
The thermoplastic, aromatic polycarbonates have average weight-average molecular weights (MW, measured e.g. by ultracentrifuge or scattered light measurement) of from 10,000 to 200,000 g/mol, preferably 15,000 to 80,000 g/mol, particularly preferably 24,000 to 32,000 g/mol. The thermoplastic, aromatic polycarbonates may be branched in a known manner, and in particular preferably by incorporation of from 0.05 to 2.0 mol %, based on the sum of the diphenols employed, of compounds which are trifunctional or more than trifunctional, for example those having three and more phenolic groups. Both homopolycarbonates and copolycarbonates are suitable.
Preferred polycarbonates are, in addition to the bisphenol A homopolycarbonates, the copolycarbonates of bisphenol A with up to 15 mol %, based on the sum of the moles of diphenols, of other diphenols mentioned as preferred or particularly preferred, in particular 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.
Aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4′-dicarboxylic acid and of naphthalene-2,6-dicarboxylic acid. Mixtures of the diacid dichlorides of isophthalic acid and of terephthalic acid in a ratio of between 1:20 and 20:1 are particularly preferred. A carbonic acid halide, preferably phosgene, is additionally co-used as a bifunctional acid derivative in the preparation of polyester carbonates. The aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids.
The aromatic polyester carbonates may be either linear or branched in a known manner (in this context see DE-A 2 940 024 and DE-A 3 007 934).
The relative solution viscosity (ηrel) of the aromatic polycarbonates and polyester carbonates is in the range of 1.18 to 1.4, preferably 1.20 to 1.32 (measured on solutions of 0.5 g polycarbonate or polyester carbonate in 100 ml methylene chloride solution at 25° C.). The thermoplastic, aromatic polycarbonates and polyester carbonates may be employed by themselves or in any desired mixture of one or more, preferably one to three or one or two thereof. Most preferably only one type of polycarbonate is used.
Most preferably the aromatic polycarbonate is a polycarbonate based on bisphenol A and phosgene, which includes polycarbonates that have been prepared from corresponding precursors or synthetic building blocks of bisphenol A and phosgene. These preferred aromatic polycarbonates may be linear or branched due to the presence of branching sites.
Polyamides which are suitable for the afore-mentioned blends of ABS- or ASA-resins are described in EP2537895A1 in paragraphs 39 to 40 to which is in particular referred.
Suitable polyamides are known homopolyamides, copolyamides and mixtures of such polyamides. They may be semi-crystalline and/or amorphous polyamides. Suitable semi-crystalline polyamides are polyamide-6, polyamide-6,6, mixtures and corresponding copolymers of those components. Also included are semi-crystalline polyamides the acid component of which consists wholly or partially of terephthalic acid and/or isophthalic acid and/or suberic acid and/or sebacic acid and/or azelaic acid and/or adipic acid and/or cyclohexanedicarboxylic acid, the diamine component of which consists wholly or partially of m- and/or p-xylylene-diamine and/or hexamethylenediamine and/or 2,2,4-trimethylhexamethylenediamine and/or 2,2,4-trimethylhexamethylenediamine and/or isophoronediamine, and the composition of which is in principle known. Mention may also be made of polyamides that are prepared wholly or partially from lactams having from 7 to 12 carbon atoms in the ring, optionally with the concomitant use of one or more of the above-mentioned starting components.
Particularly preferred semi-crystalline polyamides are polyamide-6 and polyamide-6,6 and mixtures thereof.
Known products may be used as amorphous polyamides. They are obtained by polycondensation of diamines, such as ethylenediamine, hexamethylenediamine, decamethylenediamine, 2,2,4- and/or 2,4,4-trimethylhexamethylenediamine, m- and/or p-xylylene-diamine, bis-(4-aminocyclohexyl)-methane, bis-(4-aminocyclohexyl)-propane, 3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 2,5- and/or 2,6-bis-(aminomethyl)-norbornane and/or 1,4-diaminomethylcyclohexane, with dicarboxylic acids such as oxalic acid, adipic acid, azelaic acid, azelaic acid, decanedicarboxylic acid, heptadecanedicarboxylic acid, 2,2,4- and/or 2,4,4-trimethyladipic acid, isophthalic acid and terephthalic acid.
Also suitable are copolymers obtained by polycondensation of a plurality of monomers, as well as copolymers prepared with the addition of aminocarboxylic acids such as ε-aminocaproic acid, ω-aminoundecanoic acid or w-aminolauric acid or their lactams.
Particularly suitable amorphous polyamides are the polyamides prepared from isophthalic acid, hexamethylenediamine and further diamines such as 4,4′-diaminodicyclohexylmethane, isophoronediamine, 2,2,4- and/or 2,4,4-trimethylhexamethylenediamine, 2,5- and/or 2,6-bis-(aminomethyl)-norbornene; or from isophthalic acid, 4,4′-diaminodicyclohexylmethane and ε-caprolactam; or from isophthalic acid, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane and laurinlactam; or from terephthalic acid and the isomeric mixture of 2,2,4-and/or 2,4,4-trimethylhexamethylenediamine.
The polyamides preferably have a relative viscosity (measured on a 1 wt. % solution in m-cresol or 1% (weight/volume) solution in 96 wt. % sulfuric acid at 25° C.) of from 2.0 to 5.0, particularly preferably from 2.5 to 4.0.
In particular preferred polyamides are e.g. Ultramid® grades such as Ultramid B24N 03 or Ultramid B27E commercially available from BASF SE, Germany.
The matrix polymer (I) of the afore-mentioned preferably comprises or consists of:
28 to 52 wt.-%, more preferred 35 to 45 wt.-%, most preferred 36 to 41 wt.-% polyamide (component I″), and
48 to 72 wt.-%, more preferred 55 to 65 wt.-%, most preferred 59 to 64 wt.-% ABS resin (component I′),
wherein the sum of components (I′) and (I″) totals 100% by weight.
ABS resins with polyamide are commercially available as Terblend® N grades from Styrolution company (Frankfurt, Germany).
The matrix polymer (I) of the afore-mentioned blends of ABS resins with polyamide preferably comprises or consists of:
34 to 74 wt.-%, more preferred 55 to 72 wt.-%, most preferred 58 to 70 wt.-% polyamide (component I″), and
26 to 66 wt.-%, more preferred 28 to 45 wt.-%, most preferred 30 to 42 wt.-% ABS resin (component I′),
wherein the sum of components (I′) and (I″) totals 100% by weight.
ABS resins with polycarbonate are commercially available as Novodur® Ultra grades from Styrolution company (Frankfurt, Germany).
The matrix polymer (I) of the afore-mentioned blends of ASA resins with polyamide preferably comprises or consists of:
28 to 52 wt.-%, more preferred 35 to 45 wt.-%, most preferred 36 to 41 wt.-% polyamide (component I″), and
48 to 72 wt.-%, more preferred 55 to 65 wt.-%, most preferred 59 to 64 wt.-% ASA resin (component I′),
wherein the sum of components (I′) and (I″) totals 100% by weight.
ASA resins with polyamide are commercially available as Terblend S grades, e.g. Terblend S NM-31 from Styrolution company (Frankfurt, Germany).
The matrix polymer (I) of the afore-mentioned blends of ASA resins with polyamide preferably comprises or consists of:
34 to 74 wt.-%, more preferred 55 to 72 wt.-%, most preferred 58 to 70 wt.-% polyamide (component I″), and
26 to 66 wt.-%, more preferred 28 to 45 wt.-%, most preferred 30 to 42 wt.-% ASA resin (component I′),
wherein the sum of components (I′) and (I″) totals 100% by weight.
ASA resins with polycarbonate are commercially available as Luran SC grades, e.g. Luran S KR2864C from Styrolution company (Frankfurt, Germany).
Suitable elastomeric block copolymers used as styrenic polymer (I′) for the inventive TCP resin composition are:
block copolymers of the structure (S-(B/S))_n-S, where S is a vinylaromatic—in particular styrene—block forming a hard phase, (B/S) is a random copolymer block of vinylaromatic monomer—in particular styrene—and of 1,3-diene—in particular 1,3-butadiene—forming a soft phase, and n are natural numbers from 1 to 10, preferably 1 to 4,
wherein the elastomeric block copolymer has a monomer composition comprising 25 to 60% by weight of diene, in particular 1,3-butadiene, and 75 to 40% by weight of vinylaromatic compound, in particular styrene,
the glass transition temperature Tg of block S is above 25° C. and that of block (B/S) is below 25° C., and the proportion of the hard phase in the elastomeric block copolymer is from 5 to 40% by weight and the relative amount of 1,2 linkages of the polydiene, based on the sum of 1,2- and 1,4-cis/trans-linkages, is less than 15%, preferably less than 12%.
Said block copolymers (I′) are prepared by anionic polymerization in a nonpolar solvent, initiation being effected by means of organometallic compounds. Compounds of the alkali metals, in particular of lithium, are preferred. Examples of initiators are methyl-lithium, ethyllithium, propyllithium, n-butyllithium, sec-butyllithium and tertbutyllithium. The organometallic compound is added as a solution in a chemically inert hydrocarbon.
The dose depends on the intended molecular weight of the polymer but is, as a rule, from 0.002 to 5 mol %, based on the monomers. Preferably used solvents are aliphatic hydrocarbons, such as cyclohexane and methylcyclohexane.
The random blocks of the block copolymers (I′), which blocks simultaneously contain vinylaromatic and diene, are prepared with the addition of a soluble potassium salt, in particular of a potassium alcoholate. Preferred potassium alcoholates are tertiary alcoholates of at least 7 carbon atoms and typical corresponding alcohols are, for example, 3-ethyl-3-pentanol and 2,3-dimethyl-3-pentanol in particular Tetrahydrolinalool (3,7-dimethyl-3-octanol). In the case of alkyllithium-initiated polymerization in a nonpolar solvent such as cyclohexane, the molar ratio of lithium to potassium is from about 10:1 to 40:1. The preparation of elastomeric block copolymers (I′) is described in detail in U.S. Pat. No. 6,197,889.
A preferred block copolymer (I′) is one of the general formulae S-(B/S)-S, and a particularly preferred block copolymer is one whose soft phase is divided into blocks (B/S)₁-(B/S)₂; (B/S)₁-(B/S)₂-(B/S)₁; (B/S)₁-(B/S)₂-(B/S)₃; where the blocks have different compositions or their vinylaromatic/diene ratio in the individual blocks (B/S) changes in such a way that a composition gradient (B/S)_p1<<(B/S)_p2<<(B/S)_p3. . . occurs in each segment (part-block), the glass transition temperature Tg of each part-block being less than 25° C. Such block copolymers which have within a block (B/S), for example, p repeating segments (part-blocks) with changing monomer composition can be formed by addition of p portions of the monomers, where p is an integer from 2 to 10.
A block copolymer which has a plurality of blocks (B/S) and/or S, each having a different molecular weight per molecule, is likewise preferred.
Preferred vinylaromatic compounds are styrene and furthermore alpha-methylstyrene and vinyltoluene and mixtures of these compounds. Suitable dienes are conjugated dienes preferably 1,3-butadiene and isoprene, and furthermore piperylene, 1-phenylbutadiene and mixtures of these compounds. A particularly preferred monomer combination comprises 1,3-butadiene (=butadiene) and styrene.
The (B/S) block is composed of, for example, 75 to 40% by weight of styrene and 25 to 60% by weight of butadiene. Particularly preferably, the (B/S) block has a butadiene content of from 35 to 70% and a styrene content of from 65 to 30%.
In the case of the monomer combination styrene/butadiene, the amount by weight of the diene in the total block copolymer is 15 to 65% by weight and that of the vinylaromatic component is accordingly 85 to 35% by weight. Butadiene/styrene block copolymers having a monomer composition comprising 25 to 60% by weight of diene and 75 to 40% by weight of vinylaromatic compound are particularly preferred.
The amount by weight of the soft phase composed of diene and vinylaromatic sequences—preferably 1,3-butadiene and styrene sequences—in the solid is 60 to 95%, preferably 70 to 90%, particularly preferably 80 to 90% by weight. The blocks S formed from the vinylaromatic monomers—in particular styrene—form the hard phase, the amount by weight accordingly accounts for 5 to 40, preferably 10 to 30, particularly preferably 10 to 20% by weight.
The amount by weight of the two phases can be measured by quantitative DSC (cyclic method yielding a stable, flat baseline) and solid state proton NMR relaxation (quantitative method to determine the different phases according to their softening temperature). the future phase ratio of a polymer can also be calculated from the amounts of monomers used if complete polymerization is permitted in each case and the different blocks can be assigned to phases.
The molecular weight of block S is in general from 1000 to 200,000, preferably from 3000 to 80,000, g/mol. Within a molecule, blocks S may have different molecular weights.
The molecular weight of the block (B/S) is usually from 2000 to 250,000, preferably from 5000 to 150,000, g/mol. As in the case of a block S, a block (B/S), too, may have different molecular weights within a molecule.
Very particular preferred block copolymers (I′) according to the present invention are linear styrene-butadiene block copolymers of the general structure S-(B/S)-S having, situated between the two styrene S blocks, one or more, preferably 1, 2 or 3, more preferably one (B/S)-random blocks having random styrene/butadiene distribution. The afore-mentioned linear styrene-butadiene block copolymers are commercially available as Styroflex® 2G 66 from Styrolution, Germany.

Component (II)

The thermally conductive filler material (II) used in the present invention is an electrically insulating material.
Preferably the thermally conductive filler material (II) used in the inventive TCP resin composition (ii) consists of one aluminosilicate or, according to inventive TCP resin composition (i) consists of one aluminosilicate as component (II-1) in combination with one further component (II-2) selected from the group consisting of: multi wall carbon nanotubes, graphite and boron nitride, in particular multi wall carbon nanotubes and graphite.
Preferred are inventive TCP resin compositions (i).
It was found that the filler materials (II-2) in combination with the aluminosilicate (II-1) act as synergists leading to an increased thermal conductivity of the inventive TCP resin composition (i) if the volume ratio of the filler materials (II-1) and (II-1) is 30:1 to 0.1:1, preferably 15:1 to 0.1:1, more preferably 10:1 to 0.1:1; most preferred 5:1 to 0.1.1.
The filler material (II) can comprise differently shaped particles such as spheres, flakes, rods etc.
Preferably, the average particle size (weight median diameter D₅₀) of the filler material (II) is less than 200 microns, and more preferably, less than 100 microns; as measured using mesh analysis (e.g. Retsch AS 200 jet), Transmission Electron Microscopy (TEM), dynamic image analysis (e.g. Retsch Camsizer XT) or laser light scattering (e.g. Horiba LA-300).
Preferably, the average particle size (D₅₀) of the filler material (II) is from 0.1 to 100 μm, more preferably from 0.2 to 80 μm, most preferably from 1 to 50 μm.
Particles or granules which have multi-modal size distribution in their particle size can also be used.
Aluminosilicates suitable as filler material (II) for the TCP resin composition (ii) or filler material (II-1) for the TCP resin composition (i) are based on natural occurring aluminosilicates having preferably an average particle size from 3 to 100 μm, in particular 2 to 25 μm (D50: Mass-median-diameter (MMD), determined by a Cilas laser granulometer).
Said aluminosilicates can be used without further treatment or the surface can be treated with a coupling agent, for the purpose of improving the interfacial bonding between the aluminosilicate surface and the matrix polymer (I). Examples of the coupling agent include such of the silane series, titanate series and zirconate series, preferably of the silane series, in particular preferred is methacrylsilane.
The coupling agent is preferably added to the aluminosilicate before mixing the filler material (II) with the matrix polymer (I).
Aluminosilicates suitable as filler material (II) or (II-1) for the inventive TCP resin composition (ii) or (i) are commercially available as Silatherm®, in particular Silatherm 1360-010, Silatherm 1360-400 and Silatherm 1360-400MST, from Quarzwerke Frechen.
The density of the afore-mentioned aluminosilicates is usually between 3 and 4 g/cm³.
When graphite is used as component (II-2), the graphite may be synthetically produced or naturally produced as far as it has flake shape. Naturally produced graphite is preferred.
There are three types of naturally produced graphite that are commercially available. They are flake graphite, amorphous graphite and crystal vein graphite as naturally produced graphite.
Flake graphite, as indicated by the name, has a flaky morphology. Amorphous graphite is not truly amorphous as its name suggests but is actually crystalline. Crystal vein graphite generally has a vein like appearance on its outer surface from which it derives its name.
Synthetic graphite can be produced from coke and/or pitch that are derived from petroleum or coal. Synthetic graphite is of higher purity than natural graphite, but not as crystalline.
Flake graphite and crystal vein graphite that are naturally produced are preferred in terms of thermal conductivity and dimension stability, and flake graphite is more preferred.
Especially preferred filler materials (II-2) are graphite flakes, in particular naturally produced graphite flakes, having a particle size of from about 5 to about 100 μm and preferably about 20 to about 80 μm.
The purity of the graphite ranges from 80 to 99.9% carbon; high purities of more than 99.5% carbon are preferred.
Suitable natural graphite flakes are commercially available from Alfa Aesar GmbH & Co KG, Germany and Kropfmühl GmbH, Germany.
The multi-wall carbon nanotubes (MWCNT) used as filler material (II-2) have preferably an aspect (length to thickness) ratio of more than 100, more preferably the ratio is more than 120, most preferably about 150. The average thickness (diameter, determined by transmission electron microscopy (TEM)) of the MWNT is in the range of from 5 to 40 nm, preferably 5 to 15 nm, and the average length (determined by TEM) is in the range of from 1 to 25 μm, preferably 1 to 9.5 μm, more preferably 1 to 5 μm.
The purity of the MWCNT ranges from 80 to 95% carbon, purities of 90% carbon or more are preferred.
Multiwall carbon nanotubes can be produced in multi-ton amounts via a chemical vapor deposition process using a special catalyst system. A production method for MWNT is described in EP-Patent 1 893 528 and the synthesis of a suitable catalyst system is given in U.S. Pat. No. 7,923,615.
Suitable MWNT filler materials (II-2) are commercially available from Nanocyl S.A., Belgium; Nanocyl® NC7000 being in particular preferable.
Suitable boron nitrides (BN) used as filler material (II-2) according to the invention include cubic boron nitride, hexagonal boron nitride, amorphous boron nitride, rhombohedral boron nitride, or another allotrope, as well as combinations comprising at least one of the foregoing. It may be used as powder, agglomerates, fibers, or the like, or a combination comprising at least one of the foregoing. Hexagonal boron nitride, in particular in form of platelets, is preferred.
Suitable boron nitride generally has an average particle size of 1 to 500 micrometers. Within this range boron nitride particles having sizes of greater than or equal to 3, specifically greater than or equal to 5 micrometers may be advantageously used. The average particle size (D₅₀) of the BN particle is preferably in the range of 3 to 200 micrometers, more preferably in the range of 5 to 100 micrometers, most preferably in the range of 5 to 50 micrometers. The particle size indicated here means the single BN particle or its agglomerate at any of their dimensions.
The boron nitride particles can exist in the form of agglomerates or as individual particles or as combinations of individual particles and agglomerates.
Preferably the BN has a BN purity of greater than or equal to 95 wt.-%, specifically, greater than or equal to 99.8 wt.-%.
In particular preferred according to the invention is a thermally conductive filler material (II) consisting of one aluminosilicate (II-1) in combination with graphite, multi wall carbon nanotubes or boron nitride, preferably graphite or multi wall carbon nanotubes, as filler material (II-2).
According to one preferred embodiment of the invention the thermally conductive filler material (II) consists of one aluminosilicate (II-1) in combination with graphite or multi wall carbon nanotubes as filler material (II-2), wherein the volume ratio between components (II-1) and (II-2) is 30:1 to 1:1, preferably 15:1 to 1:1, more preferred 10:1 to 1:1, most preferred 10:1 to 2:1.
According to a further preferred embodiment of the invention the thermally conductive filler material (II) consists of one aluminosilicate (II-1) in combination with boron nitride as filler material (II-2), wherein the volume ratio between components (II-1) and (II-2) is 10:1 to 0.1:1, preferably 1:1 to 0.1:1, more preferably 0.5:1 to 0.1:1.

Component (III)

Preferably, component (III) has either a wax/talcum-like appearance at normal conditions (20° C., 1013 mbar, no addition of solvents) and/or a molecular weight of not more than 5 kDa, in particular not more than 1 KDa. The component (III) may be any additive known for plastics in the art. These are exemplarily processing aids (e.g. emulsifiers, polymerization initiators, buffer substances, conventional dispersing agents, such as low-molecular-weight waxes, e.g. polyethylene waxes, or stearates, such as magnesium stearate or calcium stearate), a plasticizer, a glossing agent, an antioxidant, a metal deactivator, an antistatic agent, a flow agent, an anti-sticking agent, metal ions, fatty acids, pigments, dyes, flame retardant additives, and stabilizers, such as light stabilizer (e.g., an UV-absorber), a process stabilizer, or a radical scavenger, and a phenolic primary stabilizer.
Suitable antioxidants are sterically hindered mono- or polynuclear phenolic antioxidants, which may be substituted in various ways and also bridged via substituents. These include not only monomeric but also oligomeric compounds, which may be built up from more than one fundamental phenol unit. Hydroquinones and substituted compounds which are hydroquinone analogs are also suitable, as are antioxidants based on tocopherols and their derivatives. Mixtures of different antioxidants may also be used. In principle, it is possible to use any compound which is commercially available or suitable for styrene copolymers, such as Topanol® or Irganox®.
Alongside the phenolic antioxidants mentioned as examples above, it is possible to use costabilizers, in particular phosphorus- or sulfur-containing costabilizers. Such phosphorus- or sulfur containing costablizers are known to the person skilled in the art and are commercially available.
Examples of suitable antistats are amine derivatives, such as N,N-bis(hydroxyalkyl)alkylamines or -alkyleneamines, polyethylene glycol esters, copolymers of ethylene glycol and propylene glycol, and glycerol mono- and distearates, and mixtures of these.
Pigments are composed of solid particles less than 100 μm, preferably less than 50 μm, more preferably less than 1 μm in diameter. Examples of pigments are titanium dioxide, zinc chromate, phthalocyanines, lithopone, ultramarine blue, iron oxides and carbon black and the entire class of organic pigments.
Examples of flame retardants are the halogen-, sulfur or phosphorus-containing compounds and/or mixtures thereof known to the person skilled in the art, magnesium hydroxide and other customary compounds or mixtures of these. Red phosphorus is also suitable.
Dyes are all dyes which can be used for the transparent, semitransparent or nontransparent coloration of polymers, in particular those which are suitable for coloration of styrene based copolymers. Dyes of this type are known to the person skilled in the art.
Examples of suitable stabilizers to counter the action of light (UV-stabilizer) are various substituted resorcinols, salicylates, benzotriazoles, benzophenones and HALS (hindered amine light stabilizers), commercially available, for example, as Tinuvin®.
A component (III) as used herein may be added to the styrene copolymer composition on purpose or may result from the production process of either the polymer raw components and/or the blending process (e.g., as residual(s) from solvent(s), monomer(s), activator(s), precipitation and/or purification step(s), degradation products from monomer(s), activator(s) and/or other pyrolytic product(s)). The additive may be added upon blending the polymer raw components and/or may be comprised in one or more of the polymer raw component(s).
According to one preferred embodiment the TCP resin composition (ii) comprises (or consists of) components (I) and (II) in the following amounts:

- 45 to 60%, preferably 45 to 55% by volume of at least one of the afore-mentioned elastomeric block copolymers (I′), in particular one linear styrene-butadiene block copolymer (I′) of the general structure S-(B/S)-S having, situated between the two styrene S blocks, one (B/S)-random block having random styrene/butadiene distribution, as matrix polymer (I); and
- 40 to 55%, preferably 50 to 55% by volume of an aluminosilicate (II) as thermally conductive filler material (II);
- wherein the sum of components (I) and (II) totals 100% by volume.

According to one further preferred embodiment the TCP resin composition (i) comprises (or consists of) components (I) and (II) in the following amounts:

- 55 to 72%, preferably 55 to 65% by volume of at least one of the afore-mentioned elastomeric block copolymers (I′), in particular one linear styrene-butadiene block copolymer (I′) of the general structure S-(B/S)-S having, situated between the two styrene S blocks, one (B/S)-random block having random styrene/butadiene distribution, as matrix polymer (I); and
- 28 to 45%, preferably 35 to 45% by volume of a thermally conductive filler material (II) consisting of at least one aluminosilicate (II-1) in combination with multi wall carbon nanotubes or graphite (II-2), wherein the volume ratio between components (II-1) and (II-2) is 30:1 to 1:1, preferably 15:1 to 1:1, more preferred 10:1 to 1:1, most preferred 10:1 to 2:1;
- wherein the sum of components (I) and (II) totals 100% by volume.

- 55 to 72%, preferably 59 to 72% by volume of a blend of one of the aforementioned ABS resins (I′) with polyamide (I″) as matrix polymer (I); and
- 28 to 45%, preferably 28 to 41% by volume of thermally conductive filler material (II) consisting of at least one aluminosilicate (II-1) in combination with boron nitride (II-2), wherein the volume ratio between components (II-1) and (II-2) is 10:1 to 0.1:1, preferably 1:1 to 0.1:1, more preferably 0.5:1 to 0.1:1;
- wherein the sum of components (I) and (II) totals 100% by volume.

Preparation of TCP Resin Composition

Further subject of the invention is a process for the preparation of the inventive TCP resin composition by (x) melt-mixing of the matrix polymer (I) and, if present, optional components (III), and (y) addition and homogeneous dispersion of the filler material (II) to the melt.
The preparation of the TCP resin composition follows conventional procedure steps which are well known in the art.
The TCP resin compositions are in the form of a melt-mixed blend, wherein all of the polymeric components are well-dispersed within each other and all of the nonpolymeric ingredients are homogeneously dispersed in and bound by the polymer matrix, such that the blend forms a unified whole. The blend may be obtained by combining the component materials using any melt-mixing method. The component materials may be mixed to homogeneity using a melt-mixer such as a single or twin-screw extruder, blender, kneader, Banbury mixer, etc. to give a resin composition. Part of the materials may be mixed in a melt-mixer, and the rest of the materials may then be added and further melt-mixed until homogeneous. The sequence of mixing in the manufacture of the TCP resin composition of this invention may be such that the matrix polymer A) may be melted in one shot and the filler material B) and optional components C) may be fed from a side feeder, and the like, as will be understood by those skilled in the art. Preferably, the components are extrusion blended or compounded in a high intensity blender such as a twin-screw extruder.
The obtained TCP resin composition can be formed into shaped articles by a variety of means such as injection molding, extrusion, compression forming, vacuum forming, etc. well established in the art. Due to the high melt flow the TCP resin composition can be advantageously used in a sheet extrusion process.
A further subject of the invention is a shaped article made from the TCP resin composition.
Shaped articles comprising (or consisting of) the TCP resin composition can be used as “Cool Touch” surfaces for automobile interior, motor housings, lamp housings and electrical and electronic housings (e.g. laptop or smartphone housing) or, especially due to its high electrical resistance, as heat sinks for high performance electronics or LED sockets.
A further subject of the invention is the use of said shaped articles for the aforementioned applications.
Compared to material according to the prior art the inventive TCP resin composition shows less shrinkage and a high gloss surface. Furthermore the inventive TCP resin composition shows significant improvements in terms of processability.
The present invention is further described by the following examples and claims.

EXAMPLES

Materials:

Component (I):

ABS/PA Blend: Terblend N® NM-21EF (UV-stabilized ABS/PA blend with high impact toughness, excellent flowability and enhanced heat resistance, Styrolution, Frankfurt, Germany).
Elastomeric block copolymer: Styroflex® 2G 66 from Styrolution (Frankfurt, Germany), a linear styrene-butadiene triblock copolymer (SBC) of the structure S-(S/B)-S, the amount of the monomers in the total block copolymer is 35% by weight of butadiene and 65% by weight of styrene; the weight ratio of the blocks is 16/68/16; MFI: 14 (200° C./5 kg) g/10 min.
ABS: Terluran® HI-10 (high impact, medium flow, injection molding and extrusion grade ABS of Styrolution, Frankfurt).

Component (II):

aluminosilicate: Silatherm® Grade: 1360-400 MST (source: Quarzwerke Frechen), a natural occurring aluminosilicate treated with methacrylsilane, D₅₀=5 μm (D₁₀=1 μm, D₉₀=16 μm), density: 3.65 g/cm³
Boron nitride (BN): Mixed platelets, agglomerates, D₅₀=16 μm, density: 2.2 g/cm³(Boron nitride CFX1022 from Momentive Performance Materials Inc., USA).
Graphite: natural occurring graphite flakes, up to 325 mesh, density: 2.26 g/cm³, 99.8% purity (source: Alfa Aesar GmbH & Co KG, Germany).
MWNT: Multiwall (Carbon) Nanotubes, average diameter 9.5 nm, average length 1.5 μm, density: 2.2 g/cm³, purity: 90% carbon (source: Nanocyl S.A., NC 7000—MWCNT)
The TCP resin compositions were prepared by mixing and compounding matrix polymer A and filler material B with Haake Rheomix 600p (time: 30 min at 30 rpm, Temp. 220° C. for SBC, 240° C. for ABS, 250° C. for ABS/PA-Blend).
Samples from the obtained TCP resin compositions were prepared by hot pressing with a Carver compression molding machine 25-12-2HC
Procedure for sample preparation for measurement of the thermal conductivity with Carver heated press 25-12-2HC
Compound lumps received from the kneader Haake Rheomix 600p are placed in the middle of a sandwich consisting of a metal plate, a release foil (e.g. glass fabric enhanced PTFE), a metal spacer (1 mm thickness) for adjusting the thickness of the resultant sample, again a release foil and a metal plate. This sandwich is preheated in the Carver heated press 25-12-2HC (220-250° C. depending on utilized polymer) without applied pressure for 2 min to 4 min (depending on the time needed for softening of the respective compound). After the material has softened a pressure of 6 metric tons is applied to the sandwich for 1 min. Afterwards the sandwich is removed and placed in a water cooled press for re-cooling with an applied force of 8 kN. Finally a 1 mm thick sample piece is received for investigation of the thermal conductivity.

Measurement Methods:

Thermal conductivity κ=α·c _p·ρ:

- thermal diffusivity α: determined by Laser flash analysis (XFA 500 XenonFlash apparatus (Linseis) with an InSb infrared detector) through-plane measurement, Temp. 25° C. under air
- specific heat c_pwas determined by DSC (TA Instruments Q1000 DSC), 20 K/min, 50 ml/min N2, 10 to 30 mg sample, ASTM E1269
- temperature program:
  - 1. slope set to 200 to 215° C.
  - 2. isotherm for 10 minutes
  - 3. slope set to minus 40° C.
  - 4. isotherm for 10 minutes
  - 5. slope set to 200 to 215° C.
- density ρ is determined by Buoyancy Balance (Mettler Toledo AG245)

Table 1 shows inventive TCP resin compositions (ii) with an aluminosilicate as filler material (II) in Styroflex 2G66 as matrix polymer (I).
The amount of the filler material (II) is based on the sum of components (I) and (II) which totals 100% by volume.

TABLE 1

	Filler	thermal		heat	Thermal
	Material (II)	diffusivity	Density	capacity	conductivity
Exp. No.	Vol %	cm²/s	g/cm³	J/g*K	W/m*K

Not in-	30.3	0.00196	1.733	1.111	0.378
ventive
1	40.3	0.00296	1.985	1.011	0.596
2	53.6	0.00556	2.29	0.928	1.182

The data presented in Table 1 show that the inventive TCP resin compositions (ii) show a significantly improved thermal conductivity in comparison to not inventive TCP resin compositions.
Table 2 shows inventive TCP resin compositions (i) with Styroflex 2G66 as matrix polymer (I) and a filler material (II), a mixture of an aluminosilicate as component (II-1) and graphite (examples 6 to 8) or MWNT (examples 3 to 5) as component (II-2). The sum of components (I) and (II) totals 100% by volume.

TABLE 2

	total
	Filler (II)	Volume		Thermal		heat	Thermal
Exp.	(II-1) + (II-2)	Ratio	Component	diffusivity	Density	capacity	conductivity
No.	Vol %	(II-1):(II-2)	(II-2)	cm²/s	g/cm³	J/g*K	W/m*K

3	40.3	30:1	MWNT	0.00360	2.02	1.106	0.803
4	40.3	10:1	MWNT	0.00402	1.9788	1.092	0.868
5	40.3	5:1	MWNT	0.00492	1.9266	1.038	0.983
6	40.3	30:1	Graphite	0.00288	2.0097	1.060	0.613
7	40.3	10:1	Graphite	0.00301	1.9876	1.106	0.661
8	40.3	5:1	Graphite	0.00323	1.9439	1.023	0.643

Table 3 shows inventive TCP resin compositions (i) with Terblend N NM21-EF as matrix polymer (I) and a filler material (II), a mixture of an aluminosilicate as component (II-1) and boron nitride as component (II-2). The sum of components (I) and (II) totals 100% by volume.

TABLE 3

	total			TiO₂
	Filler (II)	Volume		Component	Thermal		heat	Thermal
Exp.	(II-1) + (II-2)	Ratio	component	(III)	diffusivity	Density	capacity	conductivity
No.	Vol %	(II-1):(II-2)	(II-2)	wt-%	cm²/s	g/cm³	J/g*K	W/m*K

9	28.8	0.18:1	BN CFX1022	1	0.00646	1.834	0.919	1.089
10	29.8	0.35:1	BN CFX1022	1	0.00469	1.855	0.936	0.813

The data in Tables 2 and 3 show that graphite, MWNT and BN act synergistically with the aluminosilicate. The inventive TCP resin compositions (i) with Styroflex 2G66 as matrix polymer (I) and a mixture of an aluminosilicate as component (II-1) and graphite as component (II-2) (examples 6 to 8), MWNT (examples 3 to 5) or BN (examples 9 to 10) as component (II-2) show a synergistically improved thermal conductivity in comparison to the composition of example 1.

Examples 11 to 14

TABLE 4

TCP resin compositions

Exp.	Component	Component	Component	Additive
No.	(I)	(II-1)	(II-2)	(III)

11	46 vol.-%	54.0 vol.-%	—	—
	ABS/PA-	aluminosilicate,
	blend	(80 wt.-%)
12	60 vol.-%	36.4 vol.-% BN	3.6 vol.-%	2 wt.-% TiO₂
	ABS	(64.1 wt.-%)	aluminosilicate,
			(5.9 wt.-%)
13	60 vol.-%	36.4 vol.-% BN	3.6 vol.-%	2 wt.-% TiO₂
	ABS/PA-	(63.4 wt.-%)	aluminosilicate
	blend		(5.9 wt.-%)
14	60 vol.-%	36.4 vol.-% BN	3.6 vol.-%	2 wt.-% TiO₂
	SBC	(64.7 wt.-%)	aluminosilicate
			(6.0 wt.-%)

The amount of the additive (III) is based on the entire resin composition.
The TCP resin composition (ii) of Example 11 was produced using a MKS-30 Buss kneader with a Scheer SGS 25-E4 granulator. The total throughput was 4.25 kg/h, the speed was 70 rpm, the granulator feed was 50 m/min, the feed was in zone 1, the temperature was between 290° C. (zones 1 to 3), 280° C. (zone 4) and 265° C. (zones 5 to 8).
The TCP resin compositions (i) of Examples 12 to 14 have been prepared by use of a ZSK26Mcc (D=26 mm, L/D=44) twin-screw extruder (Coperion GmbH, Germany). Due to the high filler level a special dosing apparatus was used according to the Feed Enhancement Technology (FET) (melt temperature: 272° C./285° C./242° C., total throughput: 20/25/20 kg/h, melt pressure: 16/15/24 bar, screw speed: 250/350/250 1/min, temperature (zones 1 to 12): 250° C./220° C./260° C. (all data refer to examples 12/13/14 in this order)).

Mechanical Characterization

Injection molding of dog bones (170 mm*10 mm*4 mm) and Charpy samples (80 mm*10 mm*3 mm) with Arburg 320 S Allrounder 500-150
(T(melt): 220° C. (example 14), 260° C. (example 12), 270° C. (examples 11, 13);
T(mold): 50° C. (example 14), 80° C. (example 12, Charpy sample); 95° C. (dog bones, examples 12, 13), 120° C. (example 11).

- un-notched Charpy impact strength was determined according to ISO 179/1eU
- Impact pendulum Zwick/Roell RKP 5113 (50 J hammer)

Tensile test: E-modulus was determined according to DIN EN ISO 527
Test of tensile properties such as Tensile modulus (=E-modulus), Breaking stress and Breaking strain with Universal testing machine Zwick Z020 with macro displacement transducer (speed for tensile modulus: 1 mm/min; rest of test: 50 mm/min).
Sample plates (70 mm*70 mm*4 mm) were used to determine thermal conductivity (determination as described above); injection molding was done under the following conditions:

- Example 11: machine: Battenfeld, screw diameter 45 mm;

T(melt) 270° C., T(mold) 90° C., injection speed 75 cm³/s, melt pressure 100 bar, packing pressure 1650 bar/10 s, cooling time 35 s

- Examples 12/13/14: machine: Engel e-mac 50, screw diameter 30 mm;
  - T(melt) 260° C./260° C./220° C. T(mold) 90° C./90° C./50° C., injection speed 100/95/75 cm³/s, melt pressure 100/100/100 bar, packing pressure 950 bar/10 s//950 bar/12/s//750 bar/10 s, cooling time 25/20/25 s (all data refer to examples 12/13/14 in this order)).

Flow Curve and Shrinkage Evaluation

- Instrument: Rheograph 6000 (Gottfert)
- Measurement parameters: Temperature selected based on polymer:
  - Styroflex 2G66 (200° C.)
  - Terluran HI10 (250° C.)
  - Terblend N (250° C.)
- Procedure
  - a) Measurement of the flow curve. This gives the actual shear rate for the utilized dye geometry (30 mm length, 1 mm diameter) and the selected two piston speeds during the melt density measurements.
  - b) Measurement of the melt density:
  - The column of the capillary rheometer is filled with the respective material, compressed by the stamp followed by a temperature equilibration. Afterwards the material is extruded through the die with the respective piston speeds. During the extrusion several material samples extruded between different fill levels are collected. With the known extruded fill level height and the column diameter the extruded volume is known. Together with the weight of the extruded sample the density in the molten state under the respective actual shear in the column is received.
  - Calculation of Shrinkage:

$Shrinkage [\frac{ρ}{ρ}] - \frac{density (RT) - density (melt)}{density (RT)} * 100 %$
The Melt Volume Rate (MVR) was measured according to DIN EN ISO 1133-1:2012-03.
Vicat Softening Temperature (VST B50): 50 N load, heating rate 50 K/h, DIN ISO 306

TABLE 5

Thermal properties:

		Thermal	Heat
Exp.	kappa	diffusity	capacity
No.	[W/mK]	[cm²/s]	[J/gK]

11	1.664	0.00742	0.932
12	0.968	0.00556	0.812
13	1.579	0.00797	0.914
14	0.991	0.00486	0.952

TABLE 6

Mechanical properties

							MVR		specific volume
	Charpy	Tensile	Breaking	Breaking			250/21.6		resistivity
Exp.	unnotched	modulus	stress	strain	Shrinkage	Density	[ml/10	VST B50	DIN IEC 60093
No.	[kJ/m²]	[Mpa]	[Mpa]	[%]	[%]	[g/cm³]	min]	[° C.]	[Ohm*m]

11	10	11700	56.6	0.78		2.408		184.7	2.13E+14
12	3.59	8960	33.2	0.4	2.9	2.142	0.05	94.9	2.57E+15
13	3.62	9280	40	0.5	3.8	2.165	1.74	—	1.56E+14
14	46.46	134	5.47	120		2.140		—	1.24E+15

Results:

Examples 11 to 14 show that TCP according to the present invention can be produced using different styrenic polymers as matrix. All examples in Table 5 show high thermal conductivity. Further Table 6 shows that a broad secondary property (e.g. Charpy unnotched, tensile modulus, MVR, VST) profile is possible, while retaining high thermal conductivity. In addition examples 11 to 14 have high specific volume resistivity as expected for electrically insulating materials. The observed shrinkage in case of example 12 and 13 is lower compared to commercially available TCPs (above 6), which is beneficial for injection molding applications.

Claims

1-13. (canceled)

14. A thermally conductive polymer (TCP) resin composition (i) or (ii) comprising components (I) and (II):

(i) 40 to 72% by volume of at least one matrix polymer (I) as component (I);

28 to 60% by volume of a thermally conductive filler material (II) as component (II) having a weight median particle diameter (D₅₀) of from 0.1 to 200 μm, which consists of at least one aluminosilicate as component (II-1) in combination with at least one further component (II-2) selected from the group consisting of: multi wall carbon nanotubes, graphite and boron nitride,

wherein the volume ratio between components (II-1) and (II-2) is from 30:1 to 0.1:1;

or

(ii) 40 to 65% by volume of at least one matrix polymer (I) as component (I);

35 to 60% by volume of a thermally conductive filler material (II) as component (II) having a weight median particle diameter (D₅₀) of from 0.1 to 200 μm which consists of at least one aluminosilicate;

wherein the matrix polymer (I) comprises styrenic polymers (I′) selected from the group consisting of: ABS (acrylonitrile-butadiene-styrene) resins, ASA (acrylonitrile-styrene-acrylate) resins, and elastomeric block copolymers of the structure

(S-(B/S))_n-S,

where S is a vinylaromatic block forming a hard phase, (B/S) is a random copolymer block of vinylaromatic monomer and of a conjugated diene forming a soft phase, and n are natural numbers from 1 to 10, wherein the elastomeric block copolymer has a monomer composition comprising 25 to 60% by weight (based on the elastomeric block copolymer) of diene and 75 to 40% by weight (based on the elastomeric block copolymer) of vinylaromatic compound, the glass transition temperature Tg of block S is above 25° C. and that of block (B/S) is below 25° C., and the proportion of the hard phase in the elastomeric block copolymer is from 5 to 40% by weight and the relative amount of 1,2 linkages of the polydiene, based on the sum of 1,2- and 1,4-cis/trans-linkages, is less than 15%; and

wherein the sum of components (I) and (II) totals 100% by volume, and

wherein the surface of the aluminosilicate is treated with a coupling agent.

15. The thermally conductive polymer (TCP) resin composition (i) or (ii) according to claim 14, having a thermal conductivity κ of more than 0.5 W/m·K.

16. The TCP resin composition according to claim 14, wherein the matrix polymer (I) comprises at least one further thermoplastic polymer (I″) selected from the group consisting of: polycarbonates and polyamides.

17. The TCP resin composition according to claim 14, wherein the matrix polymer (I) is selected from the group consisting of: ABS resins, ASA resins, elastomeric block copolymers of the structure (A-(B/A))_n-A, blend of ABS resins with polycarbonate, blend of ABS resins with polyamide, blend of ASA resins with polycarbonate, and blend of ASA resins with polyamide.

18. The TCP resin composition (i) according to claim 14 comprising 55 to 72% by volume of component (I) and 28 to 45% by volume of component (II).

19. The TCP resin composition (i) according to claim 14 wherein component (II-2) is multi wall carbon nanotubes or graphite.

20. The TCP resin composition (i) according to claim 19 comprising 55 to 65% by volume of component (I) and 35 to 45% by volume of component (II).

21. The TCP resin composition (i) according to claim 19 wherein the volume ratio between components (II-1) and (II-2) is from 30:1 to 1:1.

22. The TCP resin composition (i) or (ii) according to claim 14 wherein the matrix polymer (I) consists of an elastomeric linear styrene-butadiene block copolymer of the general structure S-(B/S)-S having, situated between the two styrene S blocks, one (B/S)-random block having random styrene/butadiene distribution.

23. The TCP resin composition (i) according to claim 14 wherein component (II-2) is boron nitride and the volume ratio between components (II-1) and (II-2) is from 10:1 to 0.1 to 1.

24. A process for the preparation of the TCP resin composition (i) or (ii) according to claim 14 by (x) melt-mixing of the matrix polymer (I), and (y) addition and homogeneous dispersion of the filler material (II) to the melt.

25. A shaped article comprising the TCP resin composition (i) or (ii) according to claim 14 formed by injection molding, extrusion, compression forming, vacuum forming, or blow molding.

26. A method of using the shaped article according to claim 25 for surfaces for automobile interior, motor housings, lamp housings and electrical and electronic housings or as heat sinks for high performance electronics or LED sockets.